CN103253862A - Low-alkali low-melting-point optical glass and preparation method thereof - Google Patents

Low-alkali low-melting-point optical glass and preparation method thereof Download PDF

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CN103253862A
CN103253862A CN2013102078398A CN201310207839A CN103253862A CN 103253862 A CN103253862 A CN 103253862A CN 2013102078398 A CN2013102078398 A CN 2013102078398A CN 201310207839 A CN201310207839 A CN 201310207839A CN 103253862 A CN103253862 A CN 103253862A
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low
glass
scope
optical glass
point optical
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CN103253862B (en
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陈培
王宏志
汪庆卫
李浩业
林芸芸
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Donghua University
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Donghua University
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Abstract

The invention relates to low-alkali low-melting-point optical glass and a preparation method thereof. The low-alkali low-melting-point optical glass comprises the following components in percentage by weight: 30-65% of B2O3, 0-18% of Al2O3, 0-15% of SiO2, 5-35% of BaO, 0-26% of ZnO, 0-22% of WO3, 0-15% of Nb2O5, 15-35% of La2O3, 0-15% of Gd2O3, 0-15% of Ta2O5, 0-10% of Li2O, 0-15% of Na2O and 0-20% of K2O. The preparation method comprises the following steps: evenly mixing the raw materials, melting, casting the molten glass, annealing, and finally performing machine-shaping, The optical glass provided by the invention has low glass transition temperature, medium-low expansion coefficient and medium refracting index, contains a proper amount of rare-earth metal oxide, and contains no harmful elements such as lead, cadmium and the like. The invention is applicable to one-step compression molding of optical glass.

Description

A kind of low alkali low-melting point optical glass and preparation method thereof
Technical field
The invention belongs to low alkali low melting glass and preparation field, particularly a kind of low alkali low-melting point optical glass and preparation method thereof.
Background technology
Along with advancing by leaps and bounds of science and technology, mobile phone, the usage quantity of the optical element in the electronic products such as notebook increases by geometric progression, optical element dimension is to miniaturization, microminiaturized direction fast development, this just makes the optical element processing problems become more and more outstanding, also have higher requirement for simultaneously the processing of optical element, therefore the opticglass compression molding technology has appearred in the seventies in last century, so-called opticglass compression molding technology, utilize the process of glass from molten state to solid-state conversion to be the hot-work character of continuous reversible exactly, near glass transformation temperature Tg, to the pressurization of heating of glass and mould, the disposable optical element that reaches service requirements that opticglass is molded into, thereby abandoned traditional corase grind, correct grinding, operations such as polishing edging and centering, directly once shaped, saved the manpower that small-sized micro-optical component adds man-hour greatly, material resources have shortened process period of optical element, have reduced the cost of optical element.Because this new technology thoroughly changed traditional opticglass working method, to the pressurization of heating of glass blank and mould, disposable glass molds is pressed into the service requirements that reaches opticglass, this has just all proposed very high requirement to glass and mould.
The glass optical component compression molding technology is a complex art, the method for glass ware forming, and the kind of glass and base substrate, moulding stock and mold machining technology all are the gordian technique of glass molds in molded.For opticglass, parameters such as glass is formed, material property, the coefficient of expansion, transition temperature are the keys of mould pressing technology, the glass swelling coefficient is more low, the stress that glass produces in mold process is more little, and the mold pressing yield rate is more high, and the glass swelling coefficient is more high, in the suddenly cold and hot process before and after the compression moulding, the glass internal stress is more big, the more easy breakage of glass, thereby the big glass of the coefficient of expansion is not suitable for precise compression molding cheaply.The transition temperature of glass is low, can prolong the life-span of molding die and the qualification rate of raising product so significantly, guarantee glass optical component smooth surface, smooth or good curvature, therefore, for being suitable for this new opticglass mould pressing technology, the opticglass component that requires exploitation to make new advances, to satisfy this new technology, novel process, this new glass is formed must take into account the transition temperature of glass and the coefficient of expansion of glass, and glass transformation temperature low (less than 500 ℃) and thermal expansivity as far as possible is as far as possible little (less than 85 * 10 -7/ ℃), be suitable for the once molding formed of opticglass.
United States Patent (USP) 7,767,605 disclose a kind of component and preparation method of niobate phosphate low-melting-point point opticglass.Main ingredient is as follows: P 2O 515to35%, Nb 2O 535to60%, Na 2O0.1to is less than 15%, BaO0to and is less than 25%, Gd 2O 30to5%, K 2O0to10%, Li 2O0to10%, Bi 2O 30to15%, MgO0to10%, CaO0to10%, SrO0to10%, ZnO0to3%, SiO 20to5%, B 2O 30to5%, Al 2O 30to4%, Ta 2O 50to5%, ZrO 20to3%, TiO 20to10%, WO 30to20%and Sb 2O 30to0.1%.This patent selects for use the niobate phosphate system to prepare low-melting point optical glass, and has higher specific refractory power and chromatic dispersion, but the transition temperature of glass is not suitable for the compression molding of optical element in this patent on 600 ℃.
The disclosed glass of Japanese Patent 2012-211041 consists of 20.0-40.0wt.%B 2O 3, 1.0-10.0wt.%SiO 2, 0.1-8.0wt.%Al 2O 3, 3.0-15.0wt.%RO, 10.0-40.0wt.%R 2O, 10.0-40.0wt.%ZnO, 1.0-15.0wt.%WO 3, 12.0wt.% or Ln still less 2O 3, 0-5.0%TiO 2R wherein 2Represent Li, Na, K; R represents Mg, Ca, Sr, Ba; Ln represents Y, La, Gd, and this patent is used for the preparation of light.R in the patent 2O content is in the 10.0-40.0wt.% scope, the alkali metal content height, can reduce the transition temperature of glass, but also make the chemical stability of glass descend, thermal expansivity significantly improves, and the life-time service of this unfavorable optical element is not mentioned in the patent because the adding of alkalimetal oxide, to the influence of glass swelling coefficient, also contain TiO in the patent 2, also can reduce the stability of glass system.
Summary of the invention
Technical problem to be solved by this invention provides a kind of low alkali low-melting point optical glass and preparation method thereof, this glass has lower glass transformation temperature, middle low-expansion coefficient, medium refractive index, contain the proper amount of rare-earth metal oxide, harmful elements such as not leaded, cadmium are applicable to the once molding formed of opticglass.
A kind of low alkali low-melting point optical glass of the present invention, its component is by comprising by weight percentage: B 2O 3: 30～65%; Al 2O 3: 0～18%; SiO 2: 0～15%; BaO:5～35%; ZnO:0～26%; WO 3: 0～22%; Nb 2O 5: 0～15%; La 2O 3: 15～35%; Gd 2O 3: 0～15%; Ta 2O 5: 0～15%; Li 2O:0～10%; Na 2O:0～15%; K 2O:0～20%.
B wherein 2O 3, Al 2O 3, SiO 2The weight percent sum be 45～65%, B wherein 2O 3With Al 2O 3And SiO 2The weight ratio of sum is greater than 2; Described La 2O 3With Gd 2O 3The weight percent sum be 15～32%, La wherein 2O 3With Gd 2O 3Ratio greater than 2; Described Li 2O, Na 2O and K 2O weight percent sum is 3～25%.
B in the described glass ingredient 2O 3Preferable range: 35～50%; Al 2O 3Preferable range: 3～12%; SiO 2Preferable range: 2～8%.B 2O 3+ Al 2O 3+ SiO 2Preferable range 45～65%.B 2O 3Be the main component of glass, in glass, as the network organizer, constitute the three-dimensional network of glass, play the transition temperature of reduction glass and the effect of softening temperature, Al 2O 3Effect be to change B 2O 3Structure in glass makes B 2O 3By boron oxygen triangle body [BO 3] change into boron oxygen tetrahedron [BO 4], thereby reach the purpose of reinforced glass network structure.A spot of SiO 2Can strengthen the connection of network, reduce the suspension degree in the network, also can improve the chemical stability of glass simultaneously.
B in the described glass ingredient 2O 3Content must be greater than Al 2O 3+ SiO 2Content, and (B 2O 3)/(Al 2O 3+ SiO 2) ratio greater than 2.
Al in the described glass ingredient 2O 3+ SiO 2Preferable range 5～20%.SiO 2Content is unsuitable too high, otherwise can cause that the borate glass system produces phase-splitting or crystallization.
The preferable range of BaO in the described glass ingredient: 8～12%.BaO can strengthen the formation scope of glass, improves the material of glass, regulates specific refractory power and the thermal expansivity of glass.
The preferable range of ZnO in the described glass ingredient: 4～15%.An amount of ZnO can strengthen the formation scope of glass, reduces glass transformation temperature and thermal expansivity.
La in the described glass ingredient 2O 3Preferable range: 15～25%; Gd 2O 3Preferable range: 3～7%; La 2O 3+ Gd 2O 3Preferable range: 15～32%; La 2O 3/ Gd 2O 3Ratio should be greater than 2.La 2O 3And Gd 2O 3Introducing can improve the glass smelting condition, reduce transition temperature and the softening temperature of glass.
WO in the described glass ingredient 3Preferable range: 5～10%, Nb 2O 5Preferable range: 0～5%, Ta 2O 5Preferable range: 0～5%, purpose is to strengthen glass forming ability, guarantees that glass forms good vitreous state and stable, and can regulate specific refractory power and the transition temperature of glass.
Li in the described glass ingredient 2O preferable range: 0～6%; Na 2O preferable range: 0～10%; K 2O preferable range: 0～12%; Li 2O+Na 2O+K 2O:3～25%.Li 2O, Na 2O, K 2O is important and necessary composition of the present invention, in order to regulate the thermal expansivity of glass, regulates transition temperature and the softening temperature of glass, improves material and the flowability of glass.
The preparation method of a kind of low alkali low-melting point optical glass of the present invention comprises:
(1) each raw material is mixed, wherein boron oxide is introduced by boric acid, and aluminum oxide is introduced by aluminium hydroxide, and BaO is introduced by its carbonate, and all the other components are introduced by oxide compound separately;
(2) raw material after step (1) is obtained mixing is founded, and anneals after the glass metal casting that will melt then, and last machine-shaping gets final product.
The temperature of founding described in the step (2) is 1150～1300 ℃, and the temperature of annealing is 480～500 ℃.
The present invention selects borate salt system, by adding Al 2O 3And SiO 2Improve the connection degree of glass network, further improve the formation ability of glass by adding BaO, ZnO, strengthen the formation zone of glass, La 2O 3And Gd 2O 3Adding can improve the glass smelting condition, accelerate the clarification homogenizing of glass, the specific refractory power that particularly can regulate glass easily also can reduce the transition temperature of glass; Li 2O, Na 2O, K 2O regulates transition temperature and the softening temperature of glass in order to regulate the thermal expansivity of glass, improves material and the flowability of glass.
Beneficial effect:
Opticglass of the present invention has lower glass transformation temperature (＜500 ℃), middle low-expansion coefficient (70～85 * 10 -7/ ℃), medium refractive index (n d=1.6～1.7), contain the proper amount of rare-earth metal oxide, harmful element such as not leaded, cadmium is applicable to the once molding formed of opticglass.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1～6
According to technical characterictic described above, determine the composition (seeing Table 1) of glass.
Described low-melting point optical glass preparation method comprises the steps:
A, selection raw material: boron oxide is introduced by boric acid, and aluminum oxide is introduced by aluminium hydroxide, and BaO is introduced by its carbonate, and all the other components are introduced by oxide compound separately, and calculating prescription, weighing mix then.
B, select quartz crucible for use, and cover lid, in the globars electric furnace, to found, glass melting temperature is 1150～1300 ℃, is incubated 1.5～3 hours.
C, the glass metal that melts are cast into glass block or glass bar, put into annealing furnace and anneal, and annealing temperature is 480～500 ℃, are incubated furnace cooling after 1 hour.
Glass after d, the annealing is pressed test request machine-shaping.
Carry out the founding of glass, moulding and grinding according to the preparation for processing of above-mentioned glass, the sample after the processing is tested.The glass of embodiment is formed (weight percent) and The performance test results sees the following form:
Table 1: low melting glass component and performance
? 1 2 3 4 5 6
SiO 2 3 3 3 3 ? 3
B 2O 3 35 40 40 45 45 45
Al 2O 3 5 3 3 3 5 3
BaO 12 20 10 10 12 20
Na 2O 3 5 2 5 ? 2
K 2O 2 ? ? ? 5 ?
Li 2O 2 2 5 ? 2 5
ZnO 12 ? 10 6 4 ?
La 2O 3 15 22 22 20 20 20
Gd 2O 3 5 5 ? 5 5 ?
Ta 2O 5 4 ? ? 3 ? ?
Nb 2O 5 ? ? ? ? 2 2
WO 3 2 ? 5 ? ? ?
n d 1.65 1.68 1.65 1.63 1.64 1.64
α(×10 -7/℃) 75.7 84.2 78.7 64.5 72.7 79.5
Tg(℃) 470 464 464 475 466 458
Tf(℃) 494 492 496 509 495 488

Claims (9)

1. one kind low alkali low-melting point optical glass, its compositions in weight percentage comprises: B 2O 3: 30～65%; Al 2O 3: 0～18%; SiO 2: 0～15%; BaO:5～35%; ZnO:0～26%; WO 3: 0～22%; Nb 2O 5: 0～15%; La 2O 3: 15～35%; Gd 2O 3: 0～15%; Ta 2O 5: 0～15%; Li 2O:0～10%; Na 2O:0～15%; K 2O:0～20%.
2. a kind of low alkali low-melting point optical glass according to claim 1 is characterized in that: described B 2O 3Scope be 35～50%, Al 2O 3Scope be 3～12%, SiO 2Scope be 2～8%.
3. a kind of low alkali low-melting point optical glass according to claim 1 is characterized in that: described Al 2O 3And SiO 2The scope of weight percent sum be 5～20%, B 2O 3, Al 2O 3, SiO 2The weight percent sum be 45～65%, B wherein 2O 3With Al 2O 3And SiO 2The weight ratio of sum is greater than 2.
4. a kind of low alkali low-melting point optical glass according to claim 1, it is characterized in that: the scope of described BaO is 8～12%, the scope of described ZnO is 4～15%.
5. a kind of low alkali low-melting point optical glass according to claim 1 is characterized in that: described La 2O 3Scope be 15～25%, Gd 2O 3Scope be 3～7%, La 2O 3With Gd 2O 3The scope of weight percent sum be 15～32%, La 2O 3With Gd 2O 3Ratio greater than 2.
6. a kind of low alkali low-melting point optical glass according to claim 1 is characterized in that: described WO 3Scope be 5～10%, Nb 2O 5Scope be 0～5%, Ta 2O 5Scope be 0～5%.
7. a kind of low alkali low-melting point optical glass according to claim 1 is characterized in that: described Li 2The scope of O is 0～6%, Na 2The scope of O is 0～10%, K 2The scope of O is 0～12%, described Li 2O, Na 2O and K 2The scope of O sum is 3～25%.
8. the preparation method of low alkali low-melting point optical glass as claimed in claim 1 comprises:
(1) each raw material is mixed, wherein boron oxide is introduced by boric acid, and aluminum oxide is introduced by aluminium hydroxide, and BaO is introduced by its carbonate, and all the other components are introduced by oxide compound separately;
(2) raw material after step (1) is obtained mixing is founded, and anneals after the glass metal casting that will melt then, and last machine-shaping gets final product.
9. the preparation method of low-melting point optical glass according to claim 8, it is characterized in that: the temperature of founding described in the step (2) is 1150～1300 ℃, the temperature of annealing is 480～500 ℃.
CN201310207839.8A 2013-05-30 2013-05-30 A kind of low alkali low-melting point optical glass and preparation method thereof Expired - Fee Related CN103253862B (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103755140A (en) * 2013-12-12 2014-04-30 广州宏晟光电科技有限公司 High refractive index middle-expansion core material glass for middle-expansion optical fiber image inverter, and preparation method thereof
CN109721240A (en) * 2019-03-18 2019-05-07 成都光明光电股份有限公司 Optical glass, gas preform, optical element and optical instrument
CN110590154A (en) * 2019-10-11 2019-12-20 成都光明光电股份有限公司 Optical glass
CN112047631A (en) * 2020-08-25 2020-12-08 广东风华高新科技股份有限公司 Lead-free low-temperature sintering encapsulation glass slurry and preparation method thereof
CN112159102A (en) * 2020-10-16 2021-01-01 内蒙古科技大学 High-release-amount negative ion glass air purification material
CN115368011A (en) * 2022-09-09 2022-11-22 中国建筑材料科学研究总院有限公司 Core-shell glass with good compatibility matching for optical fiber image transmission element and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1524815A (en) * 2002-12-27 2004-09-01 Hoya株式会社 Optical glass, press-molding glass gob and optical element
CN1663923A (en) * 2004-03-02 2005-09-07 Hoya株式会社 Optical glass, precision press-molding preform, process for production thereof, optical element and process for the production thereof
WO2012014839A1 (en) * 2010-07-26 2012-02-02 株式会社オハラ Optical glass, preform material and optical element

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1524815A (en) * 2002-12-27 2004-09-01 Hoya株式会社 Optical glass, press-molding glass gob and optical element
CN1663923A (en) * 2004-03-02 2005-09-07 Hoya株式会社 Optical glass, precision press-molding preform, process for production thereof, optical element and process for the production thereof
WO2012014839A1 (en) * 2010-07-26 2012-02-02 株式会社オハラ Optical glass, preform material and optical element

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103755140A (en) * 2013-12-12 2014-04-30 广州宏晟光电科技有限公司 High refractive index middle-expansion core material glass for middle-expansion optical fiber image inverter, and preparation method thereof
CN103755140B (en) * 2013-12-12 2016-03-09 广州宏晟光电科技有限公司 Expand in high refractive index for middle expansion optical fiber image inverter core material glass and preparation method thereof
CN109721240A (en) * 2019-03-18 2019-05-07 成都光明光电股份有限公司 Optical glass, gas preform, optical element and optical instrument
CN110590154A (en) * 2019-10-11 2019-12-20 成都光明光电股份有限公司 Optical glass
CN112047631A (en) * 2020-08-25 2020-12-08 广东风华高新科技股份有限公司 Lead-free low-temperature sintering encapsulation glass slurry and preparation method thereof
CN112159102A (en) * 2020-10-16 2021-01-01 内蒙古科技大学 High-release-amount negative ion glass air purification material
CN115368011A (en) * 2022-09-09 2022-11-22 中国建筑材料科学研究总院有限公司 Core-shell glass with good compatibility matching for optical fiber image transmission element and preparation method thereof

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